Cycloalkenyl tricycloalkene copolymers and production thereof

ABSTRACT

Cycloalkenyl tricycloalkenes are novel polycyclic compounds which may include substituents such as methyl, ethyl or others. They can be prepared by reacting a substituted or unsubstituted cyclic 1,3-diene with a 2,2&#39;&#39; -dicycloalkenyl compound. The cycloalkenyl tricycloalkenes can be used to produce elastomers by copolymerization with non-conjugated polyenes and/or olefins.

United States Patent 11 1 Amiard et al. [451 Apr. 3, 1973 [54]CYCLOALKENYL TRICYCLOALKENE [56] References Cited COPOLYMERS ANDPRODUCTION THEREOF UNITED STATES PATENTS 75 Inventors; Y i p j p Bellis,3,527,739 9/1970 Valvossori ..260/80.78

sent, Billere, both of France S d k Primary ExaminerJames A. ei ecAsslgnee- 322*1 g F F Paroles Assistant Examiner-Roger S. Benjamin ourevole rance Attorney-0strolenk, Faber, Gerb & Soffen [22] Filed: Feb. 4,1971 21 Appl. No.: 112,796 [571 ABSTRACT Cycloalkenyl tricycloalkenesare novel polycyclic Related Us'Aplfl'catwn Data compounds which mayinclude subst'ituent's such as [63] Continuation-impart of Ser. No.833,696, June 16, methyl, ethyl or others. They can be prepared by 1969,6- reacting a substituted or unsubstituted cyclic 1,3-diene I with a2,2-dicycloalkenyl compound. The cycloalke- [52] us "4360/8038, 250/795260/875 nyl tricycloalkenes can be used to produce elastomers 260/882260/648 260/666 PY by copolymerization with non-conjugated polyenes [51]Int. Cl. ..C08f 17/00 and/oll Field of Search ..260/80.78, 666 PY 10Claims, No Drawings CYCLOALKENYL TRICYCLOALKENE COPOLYMERS ANDPRODUCTION THEREOF This is a continuation-in-part of application Ser.No. 833,696 now US. Pat. No. 3,655,796, issued Apr. 11, 1972, filed June16, 1969.

The present invention relates to a new series of homologous polycycliccompounds, the cycloalkenyl tricycloalkenes, which can carry varioussubstitutions. It is also concerned with a process for thepreparation ofthese new compounds and with materials produced from them.

These polycyclic compounds of the invention are of very great interestin the production 'of elastomers by copolymerization with non-conjugatedpolyenes and/or olefins. The cycloalkyl tricycloalkenes according to theinvention can be represented by the following general formula:

f tz HC ll (CH2)D HC in which each of the radicals R R R R,, which maybe the same or different, can be hydrogen, a halogen or a linear orbranched alkyl radical having from one to 10 carbon atoms, while n canbe 1 or 2 and p can be any value from 2 to 5.

Among the preferred compounds of the invention are those for which thesymbols R to R, represent hydrogen or relatively light radicals havingfrom one to six carbon atoms, such as methyl, ethyl, isopropyl andbutyl. By way of example, mention may be made of 5-cyclopen-2-en-yl-tricyclo-(5, 2, l, ')-dec-8-ene and its derivatives,6-cyclohcx-2-enyl-tricyclo-(6,2,l ,0)- undec-9-ene and its derivatives,8-cyclooct-2'-en-yltricycle-(8,2,1 ,0-)-tridec-l l-ene and itsderivatives, and -cyclopent-2'-en-yl-tricyclo-(5,2,2,0)-undec-8- ene.

The invention provides a process for the preparation of the cycloalkenyltricycloalkenes of the invention which comprises causing the reaction ofa cyclic 1,3- diene of the general formula (in which R to R have theforegoing meanings and n is l or 2) with a 2,2'-dicycloalkenyl of thegeneral formula (in which p is 2,3,4 or 5), the reaction taking place attemperatures which are between and 500 C., preferably between 150 and250 C., and at pressures which may be from one to 1,500 atmospheres.

The reaction can be carried into effect without a solvent, or in thepresence of a solvent, which latter can be a hydrocarbon, such ashexane, heptane, cyclohexane, benzene, toluene or others, or an ether,such as dioxane, or tetrahydrofuran. The ratio by weight between thesolvent and the reactants in the reaction mixture is generally between0.5 and 20 to 1.

If the reaction between the cyclic diene and the dicycloalkenyl takesplace in the absence of a solvent, a useful feature of the inventionconsists in using an excess of dienophile with respect to the diene. Themolar ratio between the dienophile and diene can vary from 1.1 to 30,but it is preferably between 3 and 12. The dienophile excess isrecovered by distillation when the reaction is completed.

The reaction time can vary from 1 to 200 hours, depending on thetemperature, but it is preferably between 10 and 40 hours.

It is advantageous for a small proportion of hydroquinone to be added tothe reaction mixture; this hydroquinone prevents oxidation of theproducts.

As the cyclic 1,3-diene which can be used in the reaction according tothe invention, cyclope'ntadiene, l-methyl cyclopentadiene, S-methylcyclopentadiene, cyclohexa-l ,3-diene, S-methyl cyclohexal ,3-diene canbe mentioned as preferred examples.

The 2,2'-dicycloalkenyls corresponding to the foregoing formula whichcan be caused to react with the dienes, include 2,2-dicyclopentenyl,2,2- dicyclohexenyl,. 2,2'-dicyclooctenyl and 2,2'- dicycloheptenyl.

A very valuable use of the cycloalkenyl tricycloalkenes according to theinvention is in the preparation of elastomers by copolymerization withnon-conjugated polyenes or olefins.

The copolymers obtained are amorphous copolymers of high molecularweight, having a degree of unsaturation which is sufficient for them tobe able to undergo the conventional sulphur vulcanization. Thesecopolymers can also be vulcanized by means of free radical generators.

After vulcanization, the new copolymers can lead to products having goodmechanical properties, particularly breaking strengths, which may behigher than kg/cm and elongations at break, which are, for example, inthe range between and 300 percent. The vulcanized elastomer is useful inthe preparationof molded articles, wire coatings, pipes and conduits,and for other industrial moldings and extruded products.

By suitable choice of the tricycloalkenes to be copolymerized and of thepolymerization conditions, it is possible to cause the mechanicalcharacteristics of the resulting elastomers to be varied at will.

The copolymerization of the cycloalkenyl tricycloalkenes of theinvention with the non-conjugated olefin or olefins and/or thenon-conjugated polyene or polyenes can be carried out by introducing theolefin or olefins and/or the polyene or polyenes into an organic liquidmedium containing at least one of the said tricycloalkenes and anappropriate catalyst system, and by maintaining them all in contactuntil the formation of copolymers of olefines and/or of polyenes withthe said cycloalkenyl tricycloalkene or tricycloalkenes. The olefinspreferably contain two to carbon atoms. The most preferred compoundsinclude ethylene and the three to 10 carbon atom alpha olefins such aspropylene and l-butene. Typical non-conjugated olefins includel,4-pentadiene and l,4-hexadiene. The polyenes are derived from theforegoing monomers.

Catalyst systems which are quite suitable comprise an organometalliccompound (A) of one or more metals of the Groups I, II, or III of thePeriodic System and a compound (B) of a transition metal of Groups IV toVIII of the said System. Preference is particularly given to catalystsystem containing organo-aluminum compounds which may or may not behalogenated, and vanadium compounds, such as for example halides andoxyhalides of compounds in which at least one of the valencies of themetal is satisfied by a hetero atom, particularly oxygen or nitrogen,bonded to an organic group (e.g., triacetylacetonate). Excellent resultsare obtained with catalyst systems which contain, for example, vanadiumtetrachloride (VClhd 3) or vanadium oxychloride (VOCl anddiethylaluminun chloride or ethylaluminum sesquichloride.

The catalyst system can even include a certain proportion of anactivator and particularly of an alkoxyalkyl halosulphate orhalosulphite, such as ethoxyethyl chlorosulphate or chlorosulphite,etc.; of a halosulphinyl or halosulphonyl thiophene, such as 2-chlorosulphonyl thiophene, 2,4-di-(chlorosulphonyl)thiophene, etc.; of ahalogenated derivative of 5,8-dioxymethylene-A-l,4-hexahydronaphthalene, such as 1,2,3,4,9,9-hexachloro-5,8-dioxomethylene-A-l ,4-hexahydronaphthalene, etc.;of a dichloroarylphosphine, such as dichlorophenylphosphine, etc.

In order to form the catalyst system, the compounds (A) and (B) may ormay not be mixed before they are introduced into the reactor. Thecatalyst can thus be preformed and possibly aged," in order to beintroduced continuously or intermittently into the mixture to bepolymerized.

The activator, if it is present, can be mixed with the catalyst beforebeing introduced into the reaction mixture; it is also possible for theactivator to be directly introduced into the mixture duringpolymerization, continuously or in fractions. In another method ofprocedure, the activator is first of all mixed with the compound orcompounds of the transition metal or metals.

The catalyst system includes quantities of compounds A and B such thatthe molar ratio between the metal of compound A and the transition metalof compound B is between one and 30 and preferably between four and 10.

The quantity of activator which may be present can vary within widelimits. In particular, it is possible to use 0.5 to 25 moles ofactivator per gram atom of transition metal, but is is however necessaryfor the reaction medium to contain more of compound A, expressed asmetal, than of activator.

It is understood that other catalyst systems suitable for thepolymerization of olefins can also be employed. It would, for example,be possible to use catalyst systems formed by mixtures of allylcompounds of metals selected from chromium, tungsten, molybdenum orzirconium, with halides, oxyhalides, ester halides or esters of metalsselected from titanium, zirconium, vanadium, chromium, molybdenum,tungsten or iron.

The copolymerization is effected in a suitable solvent, which ispreferably formed by an aliphatic, or aromatic hydrocarbon, orcycloalkane, for example, heptane, cyclohexane, benzene, or mixtures ofsuch solvents. Halogenated hydrocarbons which are neutral as regards thecatalyst can also be used, for example, chloroform, chlorobenzene,tetrachlorethylene, etc.

The olefins can themselves serve as a solvent and the copolymerizationcan, for example, be effected in liquid butene and/or propylene.

The copolymerization can be carried into effect at temperatures whichare from 5 0 to +90 C., but it is preferable to conduct the saidcopolymerization at temperatures in the region of 0 C., for example,between 1 0 and +20 C.

The pressures usually employed during the polymerization vary from oneto 10 atmospheres, but it is possible to work under higher pressures.

The proportion of cycloalkenyl'tricycloalkene which is added to theolefins is so chosen that the final copolymer contains from 0.1 to 20percent by weight of tricycloalkenyl groups.

The tricycloalkene or tricycloalkenes are generally introduced all atonce into the reactor before the addition of the catalyst system. It is,however, possible for all or part of these compounds to be introducedduring the polymerization in a continuous or intermittent manner. Thecopolymerization can be conducted continuously, and in this case, thesolvent, the monomers and the catalyst system are continuouslyintroduced into a polymerization zone, in amounts such that their timein the said zone is sufficient to obtain the desired concentration ofcopolymer in the reaction mixture.

When considering the preparation of ethylene/propylene/tricycloalkenecopolymers, the lower limit for the ethylene content is not adetermining factor, but the upper limit should preferably be percent byweight in order to avoid a crystallinity of the polyethylene type. Asregards the content of alphaolefins in the amorphous copolymers, thiscan vary from 5 to 75 percent by weight. The tricycloalkene content ofthe copolymer can vary within very wide limits, for example, from 0.1 to20 percent by weight, but is is preferable for it to lie between 1 and10 percent by weight. g

In carrying the copolymerization reaction into operation, the reactionmedium is deprived of free oxygen by the passage of an inert gas, suchas nitrogen, argon, etc., before the polymerization.

The time required for the copolymerization generally varies with theworking conditions and it is usually between 30 minutes and 3 hours.

On completing the operation, the catalyst is destroyed in known manner,and the copolymer is separated from the solvent by coagulation by meansof an alcohol, by steam distillation of the solvent or by any othermethod by which it is possible to separate a polymer from solutionscontaining it.

The following Examples, which are non-limitative illustrate theinvention.

EXAMPLE 1 preparation of the cycloalkenyltricycloalkene.

20 g. (0.33 mole) of cyclopentadiene and 122 g. (0.91 mole) ofdicyclopentenyl (dienophile/diene ratio 5 2.7) are introduced into acylindrical autoclave and 50 mg of hydroquinone are added. The autoclaveis closed and it is heated to 180-185 C. for 20 hours. The reactionmedium is filtered and there are obtained 139 g. of a clear liquid whichis distilled under vacuum. Then 98 g. of dicyclopentenyl which has notreacted are eliminated between 42-44 C./4 mm. Hg. The remainder (i.e.,29.8 g.) distills between 105-110 C./3 mm. Hg. It is formed of 73percent of 5-cyclopen- 2'-enyl-tricyclo(5,2,1,0)-dec8-ene (referred toas compound M) represented by the following formula, the remainder beingtricyclopentadiene:-

The yields of the product M are 60 percent with respect to thedicyclopentenyl and percent with respect to the cyclopentadiene.

The 5-cyclopent-2 -en-yl-tricyclo-( 5 ,2,1,O -)-dec-8- ene as thusisolated has the following characteristics:

The polymerization is effected in a cylindrical glass reactor with aninternal diameter of 10 cm. and a capacity of 1,000 ml., said reactorbeing equipped with an agitator, a thermometer, two dropping funnels forthe introduction of the catalyst, a condenser with an outlet tube forgases and a gas inlet tube which is terminated near the bottom of thereactor by a ring having several openings permitting a better diffusionof the gases introduced through the inlet tube. The reactor is immersedin a thermostatically controlled bath in order to maintain itstemperature between -2 and +2 C.

Into the reactor, which is kept under a stream of nitrogen, there areintroduced 630 ml. of previously dried and degasified n-heptane and 5 g.of 5-cyclopent- 2-en-yl-tricyclo-(5,2,l ,0)-dec-8-ene.

The dropping funnels arranged above the reactor were cleansed and keptunder a nitrogen atmosphere. Two millimoles of VOCI, in 60 ml. ofanhydrous n-heptane are introduced into one funnel, while 10 millimolesof diethylaluminum monochloride (C I-l,) AlCl in 60 ml. of anhydrousn-heptane are introduced into the other funnel.

The supply of nitrogen is stopped and then a mixture of purifiedpropylene and ethylene in a molar ratio of 2:1 is introduced through thegas inlet tube, the mixture circulating at the rate of 99 standardliters per hour. After circulation of the gaseous mixture for 30minutes, the propylene to ethylene molar ratio is brought to the valueof 1 and the constituents of the catalyst are in- I troduced dropwiseover a 30 minute period.

The polymerization is stopped by adding 20 ml. of ethanol 60 minutesafter the start of the injection of the catalysts.

The polymer solution is poured into ethanol for coagulating theterpolymer.

After drying this polymer under vacuum at 40 C., there are obtained 29.7g. of a solid product having the appearance of a non-vulcanizedelastomer. Vulcanization of the copolymer:

Using a cylinder-type mixer, 100 parts by weight of the product which isobtained are mixed with 50 parts of HAF carbon black, five parts of zincoxide, two parts of sulphur, one part of mercaptobenzthiazole and twoparts of tetramethylthiuram disulphide.

The mixture is heated at C. for 60 minutes in a press.

Characteristics of the vulcanized product:

EXAMPLE 2 Preparation of the cycloalkenyl tricycloalkene:

The same operation as in Example 1 is repeated, but the autoclave isheated to 250260 C. After filtering the reaction mixture, 140 g. of aclear liquid are obtained. 100 g. of dicyclopentenyl which has notreacted are recovered by distillation. The product which remains is amixture of 86 percent of compound M and 14 percent oftricyclopentadiene.

The yields of M are 45% relatively to the dicyclopentenyl and 25 percentrelatively to the cyclopentadiene. Copolymerization:

Example 1 is repeated, but in the polymerization step, thepolymerization is stopped as soon as the catalysts have been completelyinjected.

Nineteen grams of a solid product are obtained, this having theappearance of an unvulcanized elastomer and containing 73 percent byweight of ethylene.

The terpolymer is then vulcanized, as in Example 1.

Characteristics of the vulcanized product:

Tensile strength 180 kg/cm Elongation at break Shore A hardness 80Rebound 53% EXAMPLE 3 Preparation of the cycloalkenyl tricycloalkene:

Twenty grams (0.33 mole) of cyclopentadiene and 244 g. (1.82 mole) ofdicyclopentenyl (dienophile/diene ratio 5.5) and also 100 mg. ofhydroquinone are introduced into the autoclave and heated at bydistillation, and then 35 g. of a mixture distilling between 105 and 110C./2.5-3 mm.l-lg.

This mixture contains 82% of compound M and 18 percent oftricyclopentadiene.

The yields of M relatively to the dicyclopentenyl and to thecyclopentadiene are respectively 56 and 47 percent.

The microanalysis of the isolated product M gives the following results,for the theoretical formula i 2o Found 90.03 10.17

Calculated 90.08 10.08

Copolymerization:

Characteristics of the vulcanized product:

Tensile strength 210 kg/cm Elongation at break 260% Shore A hardness 73Rebound 53% EXAMPLE 4 Preparation of the tricycloalkene:

20 g. (0.33 mole) of cyclopentadiene, 366 g. (2.73 moles) ofdicyclopentenyl (dienophile/diene ratio 8.2) and 50 mg. of hydroquinoneare introduced into the autoclave.

The mixture is heated at 180-l 85 C. for 20 hours.

After the reaction mixture has been filtered, 376 g. of a clear liquidare obtained. By distillation, 330 g. of unreacted dicyclopentenyl arerecovered and also 41 g. of a mixture containing 75% of5-dicyclopent-2'-en-yltricyclo-(5,2,l,0-)-dec-8-ene (compound M) and 25%of tricyclopentadiene.

The yields of M relatively to the dicyclopentenyl and to thecyclopentadiene are respectively 57 and 52 percent.

Copolymerization:

The operating procedure described in Example 1 is repeated, butreplacing the heptane by benzene and using, as the catalyst system, 1.5millimoles of VCl, and 12 millimoles of ethylaluminum sesquichloride offormula 1/2 [(C H Al Cl The saturation of the solvent by thepropyleneethylene mixture is effected in 20 minutes instead of 30minutes.

The polymerization is stopped as soon as the catalysts have beencompletely injected.

In this way, 28.8 g. of terpolymer comprising 62 percent by weight ofethylene are obtained.

The terpolymer is then vulcanized as in Example 1.

Characteristics of the vulcanized product:

Tensile strength 160 kg/cm Elongation at break 190% Shore A hardness 75Rebound 49% H C C C n I R2 11% 11C wherein R,, R R and R areindividually selected from the group consisting of hydrogen, halogen andalkyl radicals of one to 10 carbon atoms, n is l or 2, and p is 2, 3, 4or 5, with at least one unsaturated compound selected from the groupconsisting of olefins and polyenes in an organic fluid medium and in thepresence of a catalyst system comprising an organometallic derivative ofat least one metal of Groups I to III of the Periodic System and avanadium compound.

2. The process of claim 1 wherein the olefin contains two to 10 carbonatoms.

3. The process of claim 1 wherein the interpolymerization is effected ata temperature of 50 to C.

4. The process of claim 1 wherein the organometallic derivative is ahalogenated aluminum alkyl and the vanadium compound is selected fromthe group consisting of vanadium halides and vanadium oxyhalides.

5. The process of claim 4 wherein the interpolymerization is effected ata temperature of -10 to 20 C., and wherein the unsaturated compound isselected from the group consisting of ethylene and alpha olefins ofthree to 10 carbon atoms.

6. An interpolymer of a cycloalkenyl tricycloalkene of the formulawherein R R R and R are individually selected from the group consistingof hydrogen, halogen and alkyl radicals of one to 10 carbon atoms, n isl or 2, and p is 2, 3, 4 or 5; ethylene; and a compound selected fromthe group consisting of alpha olefins of three to 10 carbon atoms andpolyenes; said interpolymer having a tricycloaklkene content of 01-20weight percent.

7. The interpolymer of claim 6 wherein said compound is propylene andwherein said cycloalkenyl tricycloalkene is5-cyclopent-2-en-yl-tricyclo- (5,2,l,0'-)-dec-8-ene.

8. The interpolymer of claim 6 having a tricycloalkene content of l-20weight percent.

9. The vulcanized copolymer of claim 6.

10. The process of claim 5 wherein the unsaturated compound is a mixtureof ethylene and propylene.

@ 3 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3.7255566 Dated April 3, 1913 Inventor(s) s Amiard et a1 It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

On the cover page, read Claimspriority France PV 155189 filed June 17,1968 and France PV 175 745 filed November 28, 1968 V Column 1, line 5,after "833,696" read filed June 16, 1969 line 6, delete filed June 16,1969 line 42, for "enyl" read en-yl Column 3, line 23, for (VC1hd3)"read: (VC1 Column 5, line 15, for "enyl" read en-yl Column 8, line 64,for "20" read l0 Signed and sealed this 2nd day of April 197A.

(SEAL) Attest: H

EDWARD M.FLE'ICHER",JR. c. MARSHALL 'DANN Attesting Officer Commissionerof Patents

2. The process of claim 1 wherein the olefin contains two to 10 carbonatoms.
 3. The process of claim 1 wherein the interpolymerization iseffected at a temperature of -50* to 90* C.
 4. The process of claim 1wherein the organometallic derivative is a halogenated aluminum alkyland the vanadium compound is selected from the group consisting ofvanadium halides and vanadium oxyhalides.
 5. The process of claim 4wherein the interpolymerization is effected at a temperature of -10* to20* C., and wherein the unsaturated compound is selected from the groupconsisting of ethylene and alpha olefins of three to 10 carbon atomS. 6.An interpolymer of a cycloalkenyl tricycloalkene of the formula
 7. Theinterpolymer of claim 6 wherein said compound is propylene and whereinsaid cycloalkenyl tricycloalkene is5-cyclopent-2''-en-yl-tricyclo-(5,2,1,02.6)-dec-8-ene.
 8. Theinterpolymer of claim 6 having a tricycloalkene content of 1-20 weightpercent.
 9. The vulcanized copolymer of claim
 6. 10. The process ofclaim 5 wherein the unsaturated compound is a mixture of ethylene andpropylene.